Towards the end of the 16th century, the first known hints emerge that the Lorraine region, and in particular the archbishopric of Metz, was a source of alabaster for sculpture in the principalities and bishoprics of the western part of the Holy Roman Empire. In 1587, a list of available alabaster deposits to be used for the epitaph of Magdalena zur Lippe commissioned by the Landgrave Georg I of Hessen-Darmstadt, mentions an alabaster quarry “in the land of Lorraine, four miles from Metz” exported as far as to Würzburg in present-day Northern Bavaria. Ten years later, Metz alabaster was ordered for the decoration of the Schnellenberg castle in Westphalia. Using geochemical fingerprinting, we found evidence that a common source of alabaster was used in the Metz region and further downstream, in the Mosel and Rhine valleys. Indeed, Alabaster was used broadly from the late 16th century onwards in the major episcopal towns Trier, Bonn and Cologne. We postulate that this “phantom quarry”, so far not identified in our isotopic database of historical European alabaster deposits, is identical with the one mentioned near Metz. Indeed, several alabaster-grade gypsum quarries, still mentioned in 19th century literature, could be found within a range of around 30 km around the town. We will present results of combined archival, geological and geochemical research, conducted in the framework of the Franco-German Materi-A-Net project (https://materi-a-net.uni-koeln.de/en/news/) co-funded by ANR and DFG within the FRAL program.

Water supply for irrigation is a limiting factor for agriculture in Mediterranean countries. A strategy for increasing water availability proposes to use low quality water for irrigation to avoid irrigation with precious and high cost potable water. A drawback about using waste water is the potential heavy metal accumulation in soil and foodstuff. In this study, primary or secondary treated municipal wastewater went through supplementary cleaning steps with a low-cost device and was used to irrigate tomatoes and potatoes in an experimental field in Italy. We monitored heavy metals in soil, food and processed food during three years. We measured no accumulation neither in soil, nor in food after this period. Variations of metal concentrations in soil and food were mainly due to common farm practices such as fertilisation and pesticide applications. This study demonstrates that irrigation with wastewater is achievable with a low-cost treatment device that can be used elsewhere to decrease pressure on water resources.

Gypsum alabaster as material for European sculpture emerged in the 12th century and soon rivalled marble due to its accessibility, ease of sculpting, and aesthetic qualities. Lack of clear terminology and the visual similarity of the two materials have led to a considerable amount of confusion and deliberate misnomers. Despite attempts, since early modern times, to make a clear physical and chemical distinction between both materials, mistakes persist, even in modern collections. Here we present a non-invasive, cost-effective, reliable technique to differentiate the two, using an ultra-portable near-infrared spectrometer. The characteristic NIR spectrum of gypsum alabaster over the range of 900–1700 nm strongly contrasting with the near-featureless spectra of marble, allows for a simple and straightforward differentiation of these materials. Our technique enables rapid lithological identification of complex composite sculptural ensembles. We illustrate this through two case studies: The 15th century Saint Catherine of Alexandria from Kortrijk, attributed to André Beauneveu, one of the most prominent artists of the late Middle Ages, was supposedly made of alabaster, but is in fact made of marble and restored with alabaster replacement parts. The tomb of Prince-Bishop Julius Echter in Würzburg Cathedral is an example of the variety of materials used for such monuments in the 17th century. Here we highlight a previously undocumented but extensive use of multi-coloured alabaster.

Transition from fossil fuels to renewable energies is key to reduce human CO2 emissions, in order to cope global warming. As well as the need of technological progress, this raise the needs for metal resources. Some commodities are likely to experience very strong growth of their demand over the coming decades such as Lithium (Li), Aluminum (Al), Cobalt (Co), Nickel (Ni), Copper (Cu), and Rare Earth Elements (“REE”), due to their uses in “green” energy technologies.The EU-funded “MADITRACE” project aim for the development of traceability methods and certification systems for four critical raw material (CMR): lithium, graphite, cobalt and REEs, in order to integrate sustainable provenance of materials into a Digital Product Passport (DPP) for batteries and vehicles. In the particular case of lithium, a previous study has shown that the deposit type -‘Hard rock’ or Salar- origin of a lithium material can be tracked through the supply chain up to the battery using lithium isotopic analysis1. Nevertheless, some processes can affect this signature. In addition, these analyses requires high-cost instruments and are time-consuming. In order to verify in the future the provenance of a batch of raw material, traceability tools must be resilient to processes and mixing. They should also be more democratized and faster to set-up.In this regard, the project focuses on the development of the combination of rapid and easy-to-use on-site analysis for routine screening as well as laboratory verification in case of anomalies during the provenance verification of a lithium product. This relies on conventional geo-physico-chemical analysis such as mineralogy, major and trace element compositions, as well as isotopic analysis. The methods investigated includes hyperspectral spectroscopy, IR spectroscopy, LUXREM (XRF-XRD coupling, in development) as well as conventional X-Ray Fluorescence (XRF) and X-Ray Diffraction (XRD), Laser Induced Breakdown Spectroscopy (LIBS), (Laser Ablation) Inductively Coupled Plasma Mass Spectrometry ((LA)-QQQ-ICP-MS), (Laser Ablation) Multi-Collector Inductively Coupled Plasma Mass Spectrometry ((LA)-MC-ICP-MS) and Thermal Ionization Mass Spectrometry (TIMS). Desaulty, A. M. et al. Tracing the origin of lithium in Li-ion batteries using lithium isotopes. Nat Commun 13, (2022).

Towards the end of the 16th century, the first known hints emerge that the Lorraine region, and in particular the archbishopric of Metz, was a source of alabaster for sculpture in the principalities and bishoprics of the western part of the Holy Roman Empire. In 1587, a list of available alabaster deposits to be used for the epitaph of Magdalena zur Lippe commissioned  by the Landgrave Georg I of Hessen-Darmstadt, mentions an alabaster quarry “in the land of Lorraine, four miles from Metz” exported as far as to Würzburg in present-day Northern Bavaria. Ten years later, Metz alabaster was ordered for the decoration of the Schnellenberg castle in Westphalia.   Using geochemical fingerprinting, we found evidence that a common source of alabaster was used in the Metz region and further downstream, in the Mosel and Rhine valleys. Indeed, Alabaster was used broadly from the late 16th century onwards in the major episcopal towns Trier, Bonn and Cologne. We postulate that this “phantom quarry”, so far not identified in our isotopic database of historical European alabaster deposits, is identical with the one mentioned near Metz. Indeed, several alabaster-grade gypsum quarries, still mentioned in 19th century literature, could be found within a range of around 30 km around the town. We will present results of combined archival, geological and geochemical research, conducted in the framework of the Franco-German Materi-A-Net project (https://materi-a-net.uni-koeln.de/en/news/) co-funded by ANR and DFG within the FRAL program.

Un programme de recherche étudie depuis 2010 les usages de l’albâtre en France du xive au xvie siècle. Nous proposons ici une synthèse sur le rapport entre les documents écrits et les œuvres elles-mêmes, en centrant notre propos sur le vocabulaire utilisé dans les sources, au sein desquelles l’albâtre et le marbre sont souvent confondus. En général, les analyses ont confirmé les sources textuelles (Notre-Dame-de-Mésage pour le tombeau de Philippe le Hardi, Beuda à Perpignan), voire ont permis de préciser la chronologie d’utilisation d’une carrière (Saint-Lothain à Brou). Parfois, elles les ont infirmées : c’est un autre albâtre qui est employé (Notre-Dame-de-Mésage et non Salins à Souvigny), ou bien c’est la provenance qui demeure inconnue (albâtre indéterminé, et non de Salins, pour le tombeau de Jean sans Peur). Une carrière non documentée a été identifiée (Malaucène près d’Avignon), et le mythe des albâtres de Lagny est dissipé.

In order to analyze the effect of a new gelling agent for hydraulic fracturing, fluid samples from different stages of the operation (hydraulic fracturing fluid, coil tubing, flowback and produced waters) were collected from a well in the Vaca Muerta formation in Argentina. Collected samples were analyzed for major and trace elements, first within a few days after sampling, then reanalyzed 6 months later and again 2 years after sampling. Results show that the salinity of samples increased quickly with time, from 2000 mg/L up to 43,000 mg/l a month later, due to the mixing of hydraulic fracturing fluids with formation water. No evidence of water–rock reactions was observed. Results from the later analyses showed that the composition of the samples evolved with time with a sensible decrease of concentration for most trace elements over the course of these two years (e.g. Ba from 137 mg/L to 55 mg/L, Mn from 8 mg/L to 5 mg/L) and heavy metals (e.g. As 100μg/L to 1 μf/L, Co 160μg/L to 1.4μg/L, Cr from 160μg/L to 26μg/L). Interpretation of the results shows that delayed, post-sampling, precipitation of barite in the preserved samples is the reason for such a decrease. This opens a very interesting option for mitigation and remediation of wastewaters from hydraulic fracturing as natural or even triggered precipitation of barite could involve most of the dissolved heavy metals and decrease strongly their concentrations.

The combination of managed aquifer recharge (MAR) with soil-aquifer treatment (SAT) has clear advantages for the future sustainable quality and quantity management of groundwater, especially when using treated wastewater. We built a Marthe flow and transport model of an MAR–SAT system located in a near-shore sand aquifer, for quantifying the influence of environmental factors (climate, tides, and operational conditions) on the coastal hydrosystem with regard to the fate of trace organic compounds (TrOCs). The simulations show the impact of these factors on flow rates and dilution, and thus, on the potential reactivity of TrOCs. The dilution of secondary treated wastewater (STWW) is variable, depending on the operations (feeding from infiltration ponds) and on shore proximity (dilution by saltwater). We show that, close to the ponds and during infiltration, the attenuation of TrOC concentrations can be explained by reactivity. At the natural outlet of the aquifer, the simulated average residence times ranged from about 70 to 500 days, depending upon seasonal dynamics. It is important to study TrOCs at site scale in order to anticipate the effect of natural variations on the SAT and on the fate of TrOCs.

Soil Aquifer Treatment (SAT) can provide supplementary treatment of trace organic compounds (TrOCs) such as pharmaceutical and industrial compounds present in Secondary Treated Wastewater (STWW). Concern on presence of unregulated TrOCs in natural systems has raised recently as well as the interest in SAT systems for remediation. The present study quantifies, at the field scale over35 m of lateral groundwater flow, the effectiveness of the Agon-Coutainville SAT system (Manche, Normandy, France) for TrOCs removal by sorption and biodegradation through monitoring of seven TrOCs (oxazepam, carbamazepine, benzotriazole, tolyltriazole, caffein, paracetamol, ibuprofen) and major inorganic compounds as intrinsic tracers in STWW and groundwater during a 34-day STWW infiltration experiment during operational use of the SAT. Cationic exchanges and mixing between groundwater and STWW during the experiment were highlighted by major ions and geochemical simulations. Due to the low thickness of the unsaturated zone, a 1D analytical solution of the advection-dispersion equation (ADE) was applied on chloride data. Chloride was used as conservative intrinsic tracer to calibrate the horizontal flow and transport parameters such as the aquifer dispersion coefficient (D) and the average pore water velocity (ν) allowing estimation of the groundwater residence time. Transport and attenuation of the TrOCs were simulated assuming first-order degradation constant (μ) and linear retardation coefficient (R), calibrated to simulate the observed temporal changes in the breakthrough of TrOCs. Sorption was found to play a role in the transport of TrOCs, notably for oxazepam with a higher linear retardation coefficient value of 2.2, whereas no significant differences of retardation were observed for carbamazepine, tolyltriazole, benzotriazole (1.37, 1.35, 1.36 respectively). Estimated first order degradation rate constants, between 0.03d-1 for carbamazepine and 0.09d-1 for tolyltriazole, were generally high compared to the literature, possibly due to favourable redox conditions and important microbial activities within the system. This study provides evidence of the efficiency of the Agon-Coutainville SAT system for the removal of TrOCs.

In order to analyze the effect of a new gelling agent for hydraulic fracturing, flowback water samples were collected in the Vaca Muerta formation in Argentina during the operation. Geochemical results show that the salinity of samples increased quickly with time, due to the mixing of the hydraulic fluids with the formation water. No strong evidence of water-rock reactions was observed in contrast with the classic fracturing operations using persulfate breakers. The samples were analyzed first quickly after sampling, then reanalyzed 6 months after sampling and again 2 years after sampling. Results show that the samples contained low initial content of traces elements and heavy metals and that they evolved with time with a sensible decrease of concentration for most trace elements (e.g. Ba, B, Mn) and heavy metals (e.g. As, Co, Cu, Cr). It appears that delayed, post-sampling, precipitation of barite in the preserved samples is the reason for such a decrease. Precipitation of barite scavenges dissolved traces by incorporating them into its crystallographic structure. This opens a very interesting option for mitigation and remediation of wastewaters from hydraulic fracturing as natural or even triggered precipitation of barite could involve most of the dissolved heavy metals and decrease strongly their concentrations. The other result from this study is that trace analyses on barium and sulfate rich waters have to be done as quickly as possible in order to avoid any interference by barite precipitation. A 6 months delay appears already enough for concentration of traces to visibly decrease in the samples.

Knowledge of the natural background concentrations of groundwater constituents is important for the management of groundwater resources, particularly for the assessment of groundwater contamination and the establishment of clean-up goals and regulatory target levels. In recent years, an increasing number of studies have assessed the natural background concentrations of dissolved constituents in groundwater using a variety of different methods, each with its own assumptions, advantages and limitations. The objective of this paper is to provide a methodological basis for improving the estimation of natural background concentrations of groundwater constituents. To this end, this paper critically reviews the different approaches used to determine natural background concentrations of dissolved constituents in groundwater. In addition, two regional case studies of fluoride in Canadian groundwater are presented to illustrate the estimation of background concentrations for natural groundwater constituents. The review of existing methods shows that the use of pristine groundwater samples is not possible in many cases, due to the widespread influence of human activities. The widely used pre-selection method can provide misleading results because of inadequate selection criteria and poor statistical significance associated with the reduction of the dataset. A variety of model-based methods have been developed, but these methods are all based on assumptions that cannot be verified. Relying on the user's experience and previous knowledge of the groundwater system, exploratory data analysis has many advantages and can be applied for both anthropogenic and natural constituents. The case studies show that the exploratory data analysis approach provides critical information to determine the sources of groundwater constituents and to properly delineate groundwater bodies for which background values will be established. Natural background concentrations should always be considered as theoretical values due to their spatio-temporal variability and scale dependence, and thresholds as concentration values above which further investigation is required.

Because of its ease of working in minute detail and its whiteness, gypsum alabaster was one of the preferred materials for European sculpture rivalling marble in the late Middle Ages and early modern period. Its natural deposits are spread all over Europe, from the English Midlands to the Ukraine, from the Ebro basin to Tuscany, from the Alps and the Jurassic to central Germany (Fig. 1). The close connection between natural alabaster deposits and artistic centres, which has emerged in recent work, is related to the ecological perspective currently much discussed in art history, which emphasises the convergence of nature and culture. This new approach is based on a combination of art historical, historical and natural scientific methods and has been employed in several research projects over the last decade, involving geologists, geochemists, art historians, and conservators in a network of heritage research institutions, geological surveys, and museums. Progressively, the links established by this transdisciplinary work between historical alabaster deposits and artworks outline the evolution of the networks of European “alabaster routes”, of transfer of unworked stone, art, artists and technical and artistic knowledge which confers to this heritage stone a unique role in European integration. Here we present the current state of the art on prominent historical alabaster quarries, notably in France and Germany, and research perspectives in the framework of the upcoming Franco-German Materi-A-Net project co-funded by ANR and DFG. Fig. 1 Principal alabaster deposits used for sculpture in Late Medieval and Early Modern times. Transdisciplinary network of the Materi-A-Net project.

Significance Natural gas is a key fossil fuel as the world transitions away from coal toward less polluting energy sources in an attempt to minimize the impact of global climate change. Historically, the origin of natural gas produced from conventional reservoirs has been determined based on gas compositional data and stable isotope fingerprints of methane, ethane, and higher n-alkanes, revealing three dominant sources of natural gas: microbial, thermogenic, and abiotic. In our detailed synthesis of published natural gas data from a variety of unconventional hydrocarbon reservoirs worldwide, we demonstrate that there is a previously overlooked source of natural gas that is generated by radiolysis of organic matter in shales.